The structure of supramol. complexes formed by a naphthalene-spaced tweezer mol. as host and 1,4-dicyanobenzene (DCNB), 1,2,4,5-tetracyanobenzene (TCNB), and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) as arom., electron-deficient guests is investigated by solid-state NMR and X-ray diffraction measurements. Quantum chem. calcns. using linear scaling methods are applied to predict and to assign the 1H NMR chem. shifts of the complexes. By combining expt. and theory, insights into intra- and intermol. effects influencing the proton chem. shifts of the host-guest system are provided in the solid state.